Process for killing growing plants



United States Patent 0 3 348 939 PROCESS FOR Knimt; GROWING PLANTS DeltaW. Gier, Parkville, M0., assignor to Chemagro gorporation, New York,N.Y., a corporation of New ork N0 Drawing. Filed May 18, 1964, Ser. No.368,348 6 Claims. (Cl. 71-79) ABSTRACT OF THE DISCLOSURE Acetyleniccarbonates having the formula where R is selected from the groupconsisting of hydrogen, lower alkyl, phenyl and tolyl; R is selectedfrom the group consisting of lower alkyl, lower alkenyl, phenyl,methylphenyl, and chlorophenyl; R is selected from the group consistingof lower alkyl, phenyl, methylphenyl and chlorophenyl, and R is selectedfrom the group consisting of lower alkyl, lower alkenyl, aryl of thephenyl series, chlorophenyl, cyclohexyl, furfuryl andtetrahydrofurfuryl, are efiective as herbicides.

The present invention relates to novel herbicides.

It is an object of the present invention to prepare novel post emergentherbicides.

Another object is to prepare post emergent herbicides which haveselective activity whereby weeds can be killed without injuringagricultural crops.

A further object is to prepare a herbicide which will not effect cottonbut which will kill other plants growing in a cotton patch.

An additional object is to prepare a herbicide having low mammaliantoxicity.

Still further objects and the entire scope of applicability of thepresent invention will become apparent from the detailed descriptiongiven hereinafter; it should be understood, however, that the detaileddescription and specific examples, while indicating preferredembodiments of the invention, are given by way of illustration only,since various changes and modifications within the spirit and scope ofthe invention will become apparent to those skilled in the art from thisdetailed description.

It has now been found that these objects can be obtained by applying aherbicidally effective amount of an acetylenic carbonate having theformula to growing plants. In the formula R can be hydrogen, loweralkyl, e.g., methyl or ethyl or aryl, e.g., phenyl or tolyl, R can belower alkyl, e.g., methyl, ethyl, isobutyl, octyl, 2-ethyl hexyl,- loweralkenyl, e.g. allyl, vinyl, hexenyl and octenyl, aryl, e.g., phenyl ortolyl or chloroaryl, e.g., chlorophenyl; R can be lower alkyl, aryl orchloroaryl, e.g., chlorophenyl and R; can .be alkyl, alkenyl, aryl,chloroaryl, cycloalkyl, furfuryl or tetrahydrofurfuryl. Preferably R ishydrogen, R and R are lower alkyl and R is alkyl or aryl.

The compounds employed in the present invention as post emergentherbicides can be prepared by reacting an acetylenic hydrocarboncontaining the appropriate ketone with sodium-potassium alloy to preparean alcoholate having the formula This alcoholate is then reacted with achloroformate of the formula ClfiORA a acting the appropriate alkylalkenyl ethinyl carbinol or dialkyl ethinyl carbinol with achloroformate as shown in Bavley Patents 2,791,602 and 2,791,603.

Illustrative of compounds which can be used as herbicides according tothe present invention are methyl-1,1-dimethyl prop-Z-yne-l-yl carbonate;ethyl-l,1dimethyl prop-2-ynel -yl carbonate; npropyl-1,l-dirnethylprop-2-yne-l-yl carbonate; isopropyl-1,1-dimethyl prop-2-ynel-ylcarbonate; butyl-l,l-dirnethyl prop-Z-yne-l-yl carbonate;isobutyl-1,1-dimethyl prop-2-yne-1-yl carbonate; allyl-1,l-dimethylprop-2-yne-1-yl carbonate; amyl-l,l-dimetl1yl prop-2-yne-l-yl carbonate;2-ethylhexyl-1,1-dimethyl prop-Z-yne-l-yl carbonate; phenyl-1,1-dimethylprop-2-yne-l-yl carbonate; cyclohexyl-Ll-dimethyl prop-2yne-l-ylcarbonate; p-tolyll l-dimethyl prop-2-yne-1-yl carbonate; rn-tolyl- 1l-dimethyl prop-2-ynel -yl carbonate; o-chlorophenyl-l,l-dimethylprop-Z-yne-l-yl carbonate; p-chlorophenyl-l,l-dimethyl prop-2-yne-1-ylcarbonate; tetrahydrofurfuryl-1,1-dimethyl prop-Z-yne-l-yl carbonate;furfuryl-l,l-dimethyl prop-2-yne-1-yl carbonate; n-octy-1-1,l-dirnethylprop-Z-yne-l-yl carbonate; n-amyl-l,l-dimethyl prop-2-yne-1-ylcarbonate; ethyl-l-methyl-l-ethyl prop-2-yne-1-yl carbonate;isobutyl-l-rnethyl-l-ethyl prop-2-yne-l-yl carbonate; phenyl- 1-methyll-ethyl prop-2-ynel-yl carbonate; hexyl-l-methyl-l-ethylprop-2-yne-yl carbonate; methyl-1,1-diethyl prop-2-yne-1-yl carbonate;butyl-l-diethyl prop-2-yne-l-yl carbonate;phenyl-l,l-diethy1prop-2-yne-l-yl carbonate; ethyl-l-methyl-l-isobutylprop-2-yne-1-yl carbonate; p-tolyl- 1 -methyl- 1 -is-o-butylprop-2-yne-1-yl carbonate; ethyl-1,l-diphenyl prop-Z-yne-l-yl carbonate;phenyl-1 ,l-di-phenyl prop-Z-yne-l-yl, methyl-1 methyl-1- phenylprop-2-yne-1-yl carbonate; butyl-1-methyl-l-phenyl prop-Z-yne-l-ylcarbonate; ethyl-l-ethyl-l-phenyl prop-2-yne-l-yl carbonate;isobutyl-l-ethyl-l-vinyl prop-2-yne-1-yl carbonate;n-hexy-l-l-isopropyl-1-hexenyl prop-Z-yne-l-yl carbonate;ethyl-l-methyl-l-allyl prop-Z-yne-l-yl carbonate; ethyl-1,1-dimethylbut-2-yne-l-yl carbonate; isobutyl-1,1-dimethyl but-Z-yne-l-ylcarbonate; phenyl-l ,l-dimethyl but-2-yne-1-yl carbonate;propy-l-l,1-dimethyl but-2-yne-1-yl carbonate;

the sole toxic agent in post emergent herbicidal formulations or theycan be used with othertoxic agents.

The compounds of this invention can be made into herbicidal compositionsfor use in controlling growth of vegetation by mixing with a surfaceactive dispersing agent with or without added solvent to aid indispersing in water as a carrier for application to the soil, or with asolid dispersing agent which can itself act as a carrier.

Dispersions containing a surface active agent have the advantage ofspreading the herbicide substance more effectively over the soil area.The surface active agent can be anionic, cationic or nonionic incharacter.

Typical classes of suitable surface active agentsinclude alkyl sulfonatesalts, alkylaryl sulfonate salts, alkyl sulfate salts, alkylamidesulfonate salts, alkylaryl polyether alcohols, fatty acid esters ofpolyhydric alcohols and the alkylene oxide addition products of suchesters, and addition products of long chain mercaptans and alkyleneoxides. When salts are employed they are usually sodium orpotassiumsalts. Typical examples of such surface active agents includethe sodium alkylbenzene sulfonates having 10 to 18 carbon atoms in thealkyl group, alkyl- This took 7-10 hours. The acetylide product was amixture of The theoretical amount of the appropriate chloroformate ofthe formula was dissolved in 75 ml. of toluene, placed in a flask andcooled to 79 C. with Dry Ice-acetone. Then the acetylide was added tothe chloroformatefrom adropping funnel with stirring for 30 minutes atthis temperature. The mixture was kept at 79 C. for five hours more andthen was warmed to room temperature over ten hours. The stirring wasstopped and the mixture allowed, to stand.

The product was filtered at room temperature at the water pump, theresidue washed twice with toluene and three times with ether. Thewashings were combined with the filtrate and the ether and tolueneremoved under vacuum. The properties of the products are shown in Table1 for compounds having the formula CH: O

I HC E G C O C 0 R4 TABLE 1 B.P. 760mm. Refractive Sp. gr., 0.} R4 M-P.C.) B.P. C.) C.) Index (25 C.) 25 C.

Methyl 78.3 mm.) 155 1. 4160 1.1324

167. 5 1. 4172 0. 97875 175 1. 4202 0. 9640 188 1. 4325 0. 9872 194 1.4234 0. 9513 1. 4251 0. 9410 decomposes 1. 43421 0. 9160 Example 2phenol-ethylene oxide condensation products, e.g., p-isooctylphenolcondensed with 10 ethylene oxide units,

soaps, e.g., sodium stearate and potassium oleate, sodium salt ofpropylnaphthalene sulfonic acid, di (2-ethylhexyl) ester of sodiumsulfosuccinic acid, sodium lauryl sulfate, sodium salt of the sulfonatedmonoglyceride of cocoanut fatty acids, sorbitan sesquioleate, lauryltrimethyl ammonium chloride, octadecyl trimethyl ammonium chloride,polyethylene glycol lauryl ether, polyethylene gly col esters of fattyacids and rosin acids, sodium n-methyln-oleyl taurate, Turkey red oil,sodium dibutyl naphthalene sulfonate, sodium lignin sulfonate,polyethylene glycol stearate, decaglycerol tristearate, sodiumdodecylbenzene sulfonate, tertiary dodecyl polyethylene glycol thicether(Nonionic 218), long chain ethylene oxide-propyleneoxide condensationproducts, e.g., Pluronic 61 (molecular weight 1000), sorbitansesqnioleate, polyethylene glycol ester of tall oil acids, sodium octylphenoxyethoxyethyl sulfonate, tris (polyoxyethylene) sorbitanmonostearate (Tween 60), sodium dihexyl sulfosuccinate.

Unless otherwise indicated all parts and percentages are by weight.

Example 1 The following general procedure was employed. Seven grams ofsodium-potassium eutectic alloy (70% K-30%. Na) were added to 300 ml. oftoluene under an atmosphere of nitrogen in a reaction vessel. Afterstopping the introduction of nitrogen there was added acetylene gasfroma cylinder containing acetylene dissolved in acetone. Some of theacetone was carried over. The reaction was continued until no visiblesuspended particles were noted and the mixture became translucent orcolorless. 75

ene-acetylide mixture, i.e., (or 0.154 mole of the acetylide). Themixture was allowed to warm to room temperature with stirring. Thesodium chloride and potassium chloride were filtered off and the excesstoluene stripped under vacuum. The isobuty1-1,1-dimethyl prop-2-yne-1-yl carbonate product boiled at 40-44 C. at 3 mm.

Example 3 Primary tests for post emergent herbicidal activity werecarried out in the following manner. Oats, sugar beets, radish, flax andwheat seeds were planted in soil contained in flats measuring 14"x10"x3/2. Ten to v14 days after planting and the plants had emerged from. thesoil formulations and dilutions of the test chemicals were made andapplied at rates of 20 and 5 pounds per acre of active ingredient to theplants growing in the flats.

The formulations consisted of preparing a two pound per gallon testchemical in a pre-mix with the following composition. The partsexpressed by volume.

Eight parts of a mixture of mono, diand tri-methylnaphthalenes (VelsicolAR-SOG).

One part butyl carbitol acetate. One part Triton X-161 (mixture ofp-octylphenolwhere R is selected from the group consisting of hydrogen,lower alkyl, phenyl and tolyl; R is selected from the group consistingof lower alkyl, lower alkenyl, phenyl, methylphenyl and chlorophenyl; Ris selected from the ethylene oxide adduct containing about 16 ethyleneoxide 5 group consisting of lower alkyl, phenyl and R is selected unitstogether with a sodium alkylphenyl sulfonate). from the group consistingof lower alkyl, lower alkenyl,

Appropriate dilutions in water of the formulated matearyl of the phenylseries, chlorophenyl, cyclohexyl, furrial were applied to the plantsgrowing in the flats. After furyl and tetrahydrofurfuryl. five daysobservations and records were made of the 2. A process of killinggrowing plants comprising apeifect of the test chemical on the fiveplanted crops. plying to the growing plants a herbicidally elfectiveReadings were based on a 0 to 10 scale, where 0 indiamount of anacetylenic carbonate having the formula cates no damage or effect and 10indicates a complete kill of all of the plants. O

. I II The post emergent herbicides of the present invention ICES-0000B;are shelf stable and nontoxic to higher forms of animal life.

Many of the compounds of the present invention were wherein R and R arelower alkyl and R is lower alkyl. also given a secondary screening forpost emergent herbi- 3. A process according to claim 2 wherein R and Rcidal activity. The secondary screening was carried out exare methyl,actly as in the primary testing but the tests were extended 4, A processf killin growing plants comprising to cover cucumbers, beans, corn,cotton and alfalfa. The plying to the growing plants a herbicidallyefrective rates of application of active 611611110211 in the Secondaryamount of an acetylenic carbonate having the formula screening was 10,5, 2 and 1 pounds per acre. In the following Table 2, the activeingredients had the following 1'1, (H) formula noao-r loooru (3H3 RsCHEC (|3O C OR wherein R and R are lower alkyl and R is aryl of the CH3phenyl series.

TABLE 2 R4 Lbs/acre Fl SB Ra Wh 0a Cu Be Corn Cot Al Methyl 20 7 s 6 6 25 8 2 5 0 0 10 2 3 5 0 4 4 0 2 6 5 0 0 3 0 o 2 0 1 0 0 Ethyl 20 s s 6 o2 5 1 0 o o 0 1o 6 9 5 2 0 5 6 4 4 7 5 0 5 1 0 4 0 0 0 3 0 2 0 0 0 3 0 a4 0 0 0 Propyl- 20 7 7 4 0 0 N-butyl 20 8 6 s 5 s 5 5 3 3 0 7 1o 5 1o 74 4 6 4 6 6 8 5 2 a 3 3 0 0 0 0 0 0 2 o 0 0 0 o 0 3 a 0 0 1 0 0 0 0 5 00 5 0 0 Amyl 20 8 9 7 5 7 5 5 5 0 0 4 10 6 9 6 0 5 5 4 a 4 s 5 0 2 2 o 04 4 0 a 0 1 0 0 0 2 4 0 3 4 0 o 2-ethylhexyl. 20 9 9 8 7 9 5 3 0 3 2 2Allyl 20 7 7 7 7 s Isobutyl 20 6 9 7 s 4 5 0 4 4 4 1 10 s 9 7 s s 9 s 3s 6 5 6 9 7 s 4 7 s 4 9 4 2 5 9 7 7 4 6 s 4 s 4 1 6 9 7 5 3 7 s 5 5 0Phenyl 2o 5 9 s 10 s 5 o 2 2 2 7 10 6 9 5 6 s 6 9 s 7 7 5 2 5 5 4 7 6 86 6 a 2 3 5 4 5 7 6 9 7 7 4 1 3 4 4 a 6 6 6 4 6 1 plying to the growingplants a herbicidally effective amount of an acetylenic carbonate havingthe formula 5. A process according to claim 4 wherein R and R are methyland R is phenyl.

6. A process of killing weeds growing in a cotton patch comprisingapplying to the growing weeds an 65 amount of isobutyl-1,1-dimethylprop-Z-yne-l-yl carbonate effective to kill the weeds but insufiicientto kill the cotton.

References Cited UNITED STATES PATENTS 2,603,560 7/ 1952 Stewart 712.7 X2,885,278 5/1959 Brack 712.6

LEWIS GOTTS, Primary Examiner.

75 JAMES O. THOMAS, Examiner.

1. A PROCESS OF KILLING GROWING PLANTS COMPRISING APPLYING TO THEGROWING PLANTS A HERBICIDALLY EFFECTIVE AMOUNT OF AN ACETYLENICCARBONATE HAVING THE FORMULA